Curable fluoroelastomeric compositions

ABSTRACT

Curable fluoroelastomeric compositions employable for preparing fuel hoses or O-rings for injectors comprising: 
     A) 100 phr (parts) copolymers or terpolymers based on VDF with a content in fluorine of at least 67% by weight, the VDF being comprised from 30 to 50% by weight, from 20 to 60% by weight of HFP optionally other monomeric units deriving from a monomer having ethylene unsaturation; the sum of the comonomers being 100; 
     B) 1 to 5 phr of an adduct between an accelerator and a curing agent in molar ratio from 1:2 to 1:5, the accelerator being an onio-organic compound having a positive charge, the curing agent being a di- or polyhydroxy or di- or polythiol compound; the adduct being obtained by melting of the reaction product between accelerator and curing agent in the indicated molar ratios, or by melting of the adduct mixture 1:1 added with the curing agent in the indicated amounts.

The present invention relates to curable vinylidene-fluoride copolymers having a high content in fluorine, the other comonomers deriving from fluorinated monomers with ethylene unsaturation.

More in detail the present invention relates in particular to fluoroelastomeric copolymers based on vinylidene-fluoride (VDF), hexafluoropropene (HFP), optionally in the presence of one or more comonomers ethylenically unsaturated, the F amount being higher than 67% by weight.

More particularly the invention relates to fluoroelastromeric copolymers based on VDF suitable to the preparation of fuel hoses and shaft seals.

It is known that for the preparation of these articles, fluoroelastomeric polymers are required having good resistance to motor oils and/or to petrols containing polar substances, in particular alcohols.

This property must be combined with good elastomeric properties such as compression set and good mechanical properties and good processability in molding both by compression by injection and by extrusion.

The same copolymers can be also used for preparing O-rings used in the injectors coming into contact with petrols and/or oils containing polar substances.

It is known making articles based on VDF, HFP and tetrafluoroethylene (TFE), optionally in the presence of perfluoroalkylvinylethers (PAVE), using the peroxidic curing. The disadvantage is that the compression set obtained are poor and the removal from molds is unsatisfactory.

It is also known from the previous patent application of the Applicant, EP 525687, which corresponds to U.S. Pat. No. 5,260,392, to carry out the ionic curing with known accelerators and curing agents. The drawback is that these products show mechanical properties lower than the products cured with peroxides.

To obviate these inconveniences in the art it is known to use also processing aids such as sulphones or sulphoxides. The drawback is that the addition of these products, even though they lead to an improved rubber processing, worsen the mechanical properties and depending on the accelerating system worsen also the compression set.

It is known, moreover, that the elastomeric polymers having high content of fluorine show a bad processability due to the high viscosity of the compound.

All the disadvantages of the copolymers based on VDF with low content in fluorine (less than 67% by weight), are even more stressed in case of VDF copolymers having high content in fluorine, as indicated above.

In case of copolymers or terpolymers, indeed, having high content in fluorine, the crosslinking is even more difficult and wherefore the mechanical and elastic properties and the processability of the article result poor.

It has surprisingly and unexpectedly been found that it is possible to prepare fluoroelastomeric polymers based on-VDF having a very good combination of

high mechanical properties,

low compression set,

low viscosity of the compound such as to allow an easy processing both by compression, by injection and by extrusion,

high resistance to oils and to petrols containing polar substances, such as alcohols or ethers.

This has been made possible by using ionic curing with a particular accelerating/curing system as herein defined.

Object of the present invention are curable fluoroelastomeric compositions comprising

A) 100 phr (parts) copolymers of terpolymers based on VDF having a content in fluorine of at least 67% by weight, the VDF being comprised from 30 to 50% by weight, from 20 to 60% by weight of HFP, optionally other monomeric units deriving from a monomer having ethyelene unsaturation; the sum of the comonomers being 100. In case of copolymers, the VDF ranges from 40 to 50 and HFP ranges from 50 to 60% by weight. The other comonomers are preferably from 0 to 30% of TFE and from 0 to 40% of perfuoroalkylvinylethers, preferably 0-20%;

B) 1 to 5 phr, preferably 2 to 4.5, of an adduct between an accelerator and a curing agent in molar ratio from 1:2 to 1:5, preferably 1:2 to 1:3, the accelerator being an onio-organic compound having a positive charge, the curing agent being a di- or polyhydroxy or di- or polythiol compound; the adduct being obtained by melting of the reaction product between accelerator and curing agent in the indicated molar ratios, or by melting of the adduce 1:1 added with the curing agent in the amounts to reach the 1:2 to 1:5 adduct; optionally

C) the accelerator indicated in B) in amounts from 0.05 to 0.5 phr. The onium compound used as accelerator in B) and C) and forming the adduct cation is generally selected from the following classes:

I) aminophosphonium [P(NR'R")_(n) (R¹ R² R³)_(4-n]) ⁺ wherein n is an integer from 1 to 3;

R', R" and R¹ R² R³, equal or different from each other, are alkylic, cycloalkylic, arylic, arylalkylic, oxyalkylic or polyoxyalkylic groups having a free or esterified terminal --OH function;

R' and R" contain from 1 to 7 carbon atoms and can be linked each other so as to form an heterocyclic ring with the nitrogen atom while R¹, R², R³ equal or different from each other contain from 1 to 18 carbon atoms;

II) compounds having the formula

    Q.sup.+ (R.sup.a R.sup.b R.sup.c R.sup.d).sub.4

wherein Q is selected from nitrogen, phosphorus, arsenic, antimonium;

(III) compounds having formula:

    S.sup.+ (R.sup.a R.sup.b R.sup.c).sub.3

wherein in II) and III) R^(a), R^(b), R^(c), R^(d) are selected from alkyls, aryls, alkylaryls or their combinations, two of said free radicals can be linked each other and the Q or S atom can form an heterocyclic ring. Preferred compounds are quaternary phosphonium compounds containing at least a phosphorus atom linked by four covalent simple bonds to four organic radicals, the organic radicals generally containing from 1 to 30 carbon atoms, preferably from 2 to 8. The organic radical, being linear or branched, can contain heteroatoms. Preferred compounds are triphenylbenzylphosphonium, tetrabutylphosphonium.

The accelerator can be also a blend of the compounds of the single classes I) to III), or of more compounds of the same class.

The anion forming the adduct must be a curing agent and is generally selected from the polyhydroxy or polythiol compounds comprising the following classes:

X1) A(BH)_(m)

wherein A is an arylene radical optionally substituted with alkylic groups, such radical including optionally alkyl groups has from 6 to 14 carbon atoms, B is oxygen or sulphur and m is equal to 2 or 3;

X2) HB--R^(4a) --BH

wherein R^(4a) is an alkylene or cycloalkylene radical optionally substituted with alkylic groups, such radical including optionally alkyl groups has from 6 to 18 carbon atoms and B is oxygen or sulphur; ##STR1## wherein R^(2a) is --SO--, --SO₂ --, --CO-- or a linear or branched alkylene radical containing from 1 to 9 carbon atoms and wherein the H atoms can be partially or wholly substituted with F atoms;

X4) HOCH₂ --R^(3a) --CH₂ OH

wherein R^(3a) is a perfluoropolyether or polyfluoroether chain, the average molecular weight by number Mn being from 360 to 2,000.

The accelerators forming the cation are described in the art for instance in U.S. Pat. No. 4,259,463 for aminophosphonium compounds, in U.S. Pat. No. 3,712,877 for quaternary phosphonium salts, U.S. Pat. No. 3,655,727 for quaternary ammonium salts, in EP 337705 for class III).

The preferred cations are those deriving from aminophosphonium wherein the phosphorus atom is linked to a nitrogen atom and the other three covalent bonds are formed by organic radicals wherein the carbon is linked to phosphorus.

The following compounds can be cited: ##STR2##

    [((CH.sub.3).sub.2 N).sub.3 P--CH.sub.2 --CH.sub.3 ].sup.+

    [((CH.sub.3).sub.2 N).sub.3 P--CH.sub.3 ].sup.+

    [P(N(CH.sub.3).sub.2).sub.2 (C.sub.6 H.sub.5).sub.2 ].sup.+

    [P(N(C.sub.2 H.sub.5).sub.2).sub.2 --(C.sub.6 H.sub.5).sub.2 ].sup.+

    [P(N(CH.sub.3).sub.2).sub.2 (C.sub.6 H.sub.5) (C.sub.6 H.sub.5 CH.sub.2)].sup.+

    [P(N(C.sub.2 H.sub.5).sub.2).sub.2 (C.sub.6 H.sub.5) (C.sub.6 H.sub.5 CH.sub.2)].sup.+

    [P(N(CH.sub.3).sub.2).sub.2 (C.sub.6 H.sub.5) (CH.sub.3)].sup.+

    [P(N(C.sub.2 H.sub.5).sub.2).sub.3 (C.sub.6 H.sub.5 CH.sub.2)].sup.+

The compound 1,1-diphenyl-1-benzyl -N-diethyl-phosphoramine is particularly preferred.

Among the quaternary phosphonium compounds it can be cited

    (CH.sub.3).sub.2 (C.sub.2 H.sub.5).sub.2 P.sup.+

    (C.sub.2 H.sub.5).sub.3 (C.sub.18 H.sub.37) P.sup.+

    (CycloC.sub.6 H.sub.11).sub.2 (C.sub.6 H.sub.13).sub.2 P.sup.+

    (C.sub.4 H.sub.9).sub.3 CH.sub.2 ═CH--CH.sub.2 P.sup.+

    (C.sub.4 H.sub.9).sub.4 P.sup.+

    (C.sub.6 H.sub.5).sub.3 (C.sub.6 H.sub.5 CH.sub.2)P.sup.+

    (C.sub.6 H.sub.5).sub.3 (CH.sub.3 OC.sub.2 H.sub.5)P.sup.+

    (C.sub.8 H.sub.17).sub.3 [(CH.sub.3).sub.2 NCH.sub.2 CH.sub.2 CH.sub.2 ]P.sup.+

    (C.sub.8 H.sub.17).sub.3 (HOC.sub.2 H.sub.4)P.sup.+

    .sup.+ P(C.sub.2 H.sub.5).sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 (C.sub.2 H.sub.5).sub.3 P.sup.+

Tetrabutyl phosphonium is particularly preferred.

Among anions the bisphenol compounds (class X3), wherein the R^(2a) radical is the perfluoroalkyl group from 3 to 7 carbon atoms, and the OH are in para position, are preferred. The most preferred compound is R^(2a) =--C(CF₃)₂ --.

The adduct can be prepared as follows.

The polyhydroxy or polythiol compound is reacted, in aqueous solution or in a suitable solvent, for instance methanol, wherein the accelerator is soluble, in a first step, with a basic substance, for instance NaOH, KOH, Ca(OH)₂ and tBuO⁻ K⁺, generally by using one equivalent gram of basic substance for mole of accelerator. The reaction product is then reacted in a second step with an accelerator salt, for instance a chloride. The desired salt precipitates. After filtering and drying, the product is melted which through cooling, solidifies in flakes or pellets giving the adduct utilized in the present invention. This solid form is particularly suitable for its handling and its compounding in the blends.

The polyhydroxy or polythiol compounds are used in molar ratios from 2:1 to 5:1 with respect to the accelerator.

Without being bound to any theory, it seems by IR spectra that the excess of polyhydroxy compound results linked to the cation also when this results in excess with respect to the stoichiometric, as it must be according to the present invention.

Tests carried out by the Applicant have shown that the adducts with excess of bisphenol with respect to the accelerator show superior properties if the amount of curing agent is added in excess during the adduct preparation or after the adduct achievement in molar ratios 1:1 between accelerator and curing agent, before bringing to melting the reaction mixture containing the excess of curing agent.

As a matter of fact, if the adduct in molar ratio 1:1 is prepared and the reaction product is melted and only afterwards the desired amount of curing agent is added, the improved results according to the present invention are not obtained.

The curing blend comprises moreover, in order to obtain the cured products through heating,

a) one or more acceptors of inorganic acids selected among the ones known in ionic vulcanisation of vinylidene fluoride copolymers, in amounts 1-40 parts for 100 parts fluoroelastomeric copolymer;

b) one or more basic compounds selected from those known in ionic vulcanisation of vinylidene fluoride copolymers, in amounts from 0.5 to 10 parts for 100 parts of fluoroelastomeric copolymer.

As also known, the basic compounds of point b) are usually selected from the group consisting of Ca(OH)₂, Sr(OH)₂, Ba(OH)₂, metal salts of weak acids, such as for instance carbonates, benzoates, oxalates and phosphites of Ca, Sr, Ba, Na and K and mixtures of the aforesaid hydroxides with the abovesaid metal salts.

The composition according to the present invention commonly comprises other known components, such as fillers, for instance, carbon black, silica and dyes, generally from 5 to 30 phr; and processing adjuvants, for instance plasticizers, generally from 0.1 to 5 phr.

However an advantage according to the present invention consists in that optimum results are obtained without using processing adjuvants, such as sulphones, which generally lead to a worsening of the final properties depending on the used accelerating system.

The fluoroelastomeric copolymers, as said above, are vinylidenefluoride copolymers with one or more fluorinated monomers having ethylene unsaturation. In particular the copolymers of the present invention are VDF copolymers with hexafluoropropene.

Other comonomers having ethylene unsaturation which can be used are vinylethers (PAVE) in amounts from 0 to 40% by weight, preferably 0-20%. The preferred vinylethers are per-fluoroalkylperfluorovinylethers, in particular perfluoromethylperfluorovinylether (MVE) and perfluoropropylperfluorovinylether. Utilizable perfluorovinylethers and perfluoroalkoxyvinylethers are described in U.S. Pat. No. 3,291,843.

Other comonomers which can be utilized in amounts from 0 to 30% are for instance tetrafluoroethylene and/or chlorotrifluoroethylene.

The olefinic monomers having up to 4° C. are for instance selected from ethylene and propene, the preferred being ethylene (Et), and are used in amounts from 0 to 25% by weight, preferably from 0 to 10%.

The preferred copolymers forming the object of the present invention are characterized by the following preferable composition by weight of monomeric units:

    ______________________________________                                                         % by weight                                                    ______________________________________                                         VDF               40-50%                                                       HFP                50-60%;                                                     or by the composition:                                                         VDF               30-50%                                                       HFP               20-60%                                                       TFE                10-30%;                                                     or by the composition:                                                         VDF               30-47%                                                       HFP (hexafluoropropene)                                                                          20-40%                                                       PAVE               3-20%                                                       TFE                10-30%.                                                     ______________________________________                                    

The copolymers of the invention combine a good chemical resistance with a high curing rate, essential requirement in transformation techniques such as injection molding.

Such copolymers are capable of meeting more and more severe marketing specifications, which require good resistance to alcohols and to petrols containing alcohols especially methanol.

The VDF copolymers containing olefins particularly suitable due to their high resistance to alcohols and to bases, in particular oils containing amines, contain preferably the following monomer units:

    ______________________________________                                                     % by weight                                                        ______________________________________                                                VDF    30-50%                                                                  HFP    20-58%                                                                  PAVE   0-40%                                                                   ethylene                                                                              2-15%                                                                   TFE     0-30%.                                                          ______________________________________                                    

The fluoroelastomeric copolymers according to the present invention are prepared by emulsion polymerization according to well known techniques, preferably in the presence of radicalic initiators such as for instance persulphates, perphosphates, alkaline or ammonium perborates or percarbonates, optionally in combination with reducing agents such as sulphites, bisulphites, hyposulphites, phosphites, hypophosphites of alkaline or ammonium metals, or in combination with ferrous, cupreous or silver salts, or of other easily oxidable metals. Such methods are described in Kirk Othmer, Encyclopedia of Chemical Technology, vol. 8, pag. 500 and on, 1979. As polymerization methods can be used, in particular, the mass polymerization, that in solution of organic solvents and the one in emulsion or suspension in water.

Surfactants, such as for instance ammonium perfluoro-octanoate or others known to be suitable in preparing fluoroelastomers can be present in the polymerization medium, for example ammonium perfluoro-octanoate.

Chain transfer agents can generally be used as molecular weight regulators. Among them ethyl acetate, ethyl malonate, iodided and/or brominated chain transfer agents, such as for instance the compounds having the general formula Rf(I)_(x) (Br)_(y) wherein Rf =perfluorinated hydrocarbon radical containing from 1 to 8 carbon atoms, x, y being integers comprised between 0 and 2, with at least x or y=1 and x+y is at most 2. It can also be used compounds having also some I or Br in the place of F of the perfluorinated hydrocarbon. These are known as polyiodided or polybrominated compounds. Moreover iodides and/or bromides of alkaline or alkaline-earth metals as described in European patent application No. 407937 can be used.

When the polymerization is over, the fluoroelastomer is isolated from the polymeric latex by known methods, such as coagulation by addition of electrolytes or by cooling.

The polymerization reaction is generally carried out at temperatures from 25° C. to 150° C., under pressure up to 10 MPa.

The preparation of the elastomeric copolymers according to the invention can be carried out also by polymerization in the presence of a microemulsion formed by one or more perfluoropolyoxyalkylenes and water, according to the method described in European patent application No. 250767.

The polymerization can be carried out also by using, instead of a microemulsion, an emulsion or a dispersion of perfluoropolyoxyalkylenes and water according to the method described in U.S. Pat. No. 4,789,717.

Also the emulsions and dispersions of perfluorooxyalkylenes and water described for instance in European patent applications Nos. 196904, 280312 and 360292, can be used for this purpose.

For the curing of the polymers of the invention the elastomeric composition must be heated under pressure, at a temperature from 130° C. to 230° C., preferably from 160° C. to 200° C., for a period of time comprised from 0.5 to 60 minutes and, preferably, from 1 to 15 minutes. The obtained articles can then be post-cured in stove or in oven, at atmospheric pressure, at a temperature from 130° to 300° C., preferably from 200° C. to 275° C., for a period of time from 5 to 48 hours, and, preferably, from 10 to 24 hours.

The following examples are given for illustrative purpose but do not limit the scope of the present invention.

EXAMPLES

Preparation of the adduct

2 adducts according to the present invention are prepared by starting from the accelerator indicated below and from the bisphenol AF (BAF): ##STR3##

The accelerator has the following formula: ##STR4##

The preparation of the adduct produced starting from one accelerator mole and 5 (or 2 moles in case of 1:2 ratio, 3 moles for 1:3, and 4 moles for 1:4), moles of bisphenol AF gives the adduct in the molar ratio specified above.

In a 10 1 glass reactor, equipped with a dropping funnel and a stirrer, 352.8 g (1.05 moles) of bisphenol AF are dispersed under stirring into 5 1 of water. A solution of 8.4 g (0.21 moles) of NaOH in 500 cc of water is then quickly dropped in the reactor. The reactor is kept under stirring at room temperature for 30 minutes. Then a solution of 80.5 g (0.21 moles) of amino-phosphonium dissolved in 800 cc of water is dropped under stirring in the reactor. A very thick suspension is obtained; it is kept under stirring at room temperature for 2 hours; then it is let to stay for about 4 hours. It is filtered on cloth and washed twice with overall 2 1 of water. It is dried in a vacuum stove to 50°-60° C. for 20 hours and then the reaction mixture is brought to melt by heating at 100°-120° C. and it is allowed to cool, thus obtaining the adduct 1:5 according to the present invention.

EXAMPLES 1-3

In Table 1 the formulation of 3 compounds is reported, the first of which (compound No. 1) is a composition wherein an adduct according to the present invention was not used, but, separately, the accelerator and the bisphenol AF.

In the compounds 2 and 3 the adduct prepared according to the present invention was utilized.

The fluoroelastomer is TECNOFLON® TH 340 of Ausimont, vinylidene fluoride, hexafluoropropene and tetrafluoroethylene terpolymer having a Mooney viscosity ML (1+10) at 121° C. equal to 58, whose composition is:

    ______________________________________                                                VDF         37% by weight                                                      HFP         37% by weight                                                      TFE         26% by weight                                               ______________________________________                                          (Fluorine: 70% by weight)                                                

                  TABLE 1                                                          ______________________________________                                         FORMULATION OF THE COMPOUND                                                                  Ex. 1                                                                          (cfr)    Ex. 2  Ex. 3                                                          (phr)    (phr)  (phr)                                            ______________________________________                                         Fluoroelastomer TH 340                                                                         100        100    100                                          Bisphenol AF    2.7        --     --                                           Accelerator (I) 1.35       --     --                                           Adduct (II)     --         4.5    --                                           Adduct (III)    --         --     3.5                                          MgO             3          3      3                                            Ca(OH).sub.2    6          6      6                                            MT Black        30         30     50                                           ______________________________________                                          ##STR5##                                                                       Adduct (II): molar ratio accelerator/bisphenol 1:3 obtained by melting th      reaction mixture.                                                              Adduct (III): 1:5 obtained by melting of the reaction mixture.           

Characterization of the compound of Table 1A

These blends were cured at 170° C. in press and then to a post-curing in air stove between 200° C. and 250° C. for 24 hours.

The curing evaluation was carried out by oscillating disc rheometer (ODR) of Monsanto type according to ASTM D 2084/81.

The data relating to the blends viscosity, the curing characteristics and the mechanical properties are reported in Table 1A.

                  TABLE 1A                                                         ______________________________________                                         characteristics of the compound of Table 1.                                                      Ex 1                                                                           (cfr)  Ex. 2   Ex. 3                                         ______________________________________                                         Rheometric properties                                                          Mooney Viscosity (ASTM D1646-82)                                                                   106      82      103                                       ML(1 + 10) at 121° C. (Mooney)                                          Mooney Scorch at 135° C.                                                Minimum Viscosity (in Mooney)                                                                      44       32      45                                        Time for increasing of 15 points                                               the viscosity (min) 11'45"   33'20"  30'                                       ODR 12' at 177° C., Arc +/- 3°                                   (ASTM D2084-81)                                                                ML (lbf · in)                                                                             16       13      16                                        MH (lbf · in)                                                                             72       108     96                                        ts2 (sec)           123      141     168                                       t90 (sec)           249      270     333                                       v.sub.max (lbf · in/sec)                                                                  0.8      1.8     1.2                                       Mechanical properties (ASTM D412-83)                                           Post cure @ 250° C. × 8 + 16 hours                                Modulus 100% (MPa)  6.6      7.9     6.9                                       Tensile stress (MPa)                                                                               13.5     16      15.5                                      Elongation at break (%)                                                                            228      181     219                                       Hardness Shore A    82       82      85                                        Compression Set 70 h at 200° C.                                                             66       31      32                                        (ASTM D 395 Method B)                                                          O-rings 214 (%)                                                                ______________________________________                                    

From the above results it is noticed that the viscosity decreases by indicating an improved processability; the scorch increases therefore indicating a greater compound safety; the curing (ODR) shows a greater crosslinking yield (MH) and higher curing rate (v_(max)). The balance of the mechanical properties is surprisingly very satisfactory: a higher tensile stress/elongation ratio is obtained. The compression set is unexpectedly improved to a great extent.

EXAMPLES 4-5

Examples 1-3 were repeated using a fluoroelastomer TECNOFLON® T428E of Ausimont: terpolymer of vinylidenefluoride, hexafluoropropene and tetrafluoroethylene, having a Mooney ML (1+10) viscosity at 121° C. equal to 20, whose composition is:

    ______________________________________                                                VDF         45% by weight                                                      HFP         33% by weight                                                      TFE         22% by weight                                               ______________________________________                                          (Fluorine: 68.5% by weight); [η].sub.MEK.sup.30° C. = 55            (intrinsic viscosity).                                                   

The formulations are reported in Table 2 and the characteristics are reported in Table 2A.

                  TABLE 2                                                          ______________________________________                                         COMPOUNDS FORMULATION                                                                           EX. 4                                                                          (cfr) EX. 5                                                                    (phr) (phr)                                                   ______________________________________                                         Fluoroelastomer NMA2                                                                              100     100                                                 Bisphenol AF       1.5     --                                                  Accelerant (I)     0.6     --                                                  Adduct (II)        --      2                                                   MgO                3       3                                                   Ca(OH).sub.2       6       6                                                   MT Black           30      30                                                  ______________________________________                                    

                  TABLE 2A                                                         ______________________________________                                         characteristics of the compound of Table 1.                                                          Ex. 4                                                                          (cfr) EX. 5                                              ______________________________________                                         Rheometric properties                                                          Mooney Viscosity (ASTM D 1646-82)                                                                      39      39                                             ML(1 + 10) at 121° C. (in Mooney)                                       Mooney Scorch at 135° C.                                                Minimum Viscosity (in Mooney)                                                                          14      13                                             Time for increasing of 15 points                                                                       37'30"  40'30"                                         the viscosity (min)                                                            ODR 12' at 177° C. Arc +/- 3° (ASTM D2084-81)                    ML (lbf · in)  4       4                                              MH (lbf · in)  44      52                                             ts2 (sec)               195     168                                            t90 (sec)               285     237                                            v.sub.max (lbf · in/sec)                                                                      0.8     1.4                                            Mechanical properties (ASDTM D412-83)                                          Post curing @ 250° C. × 8 + 16 hours                              Modulus 100% (MPa)      2.5     4.0                                            Tensile strength (MPa)  12      14                                             Elongation at break (%) 329     286                                            Hardness Shore A        63      62                                             Compression Set 70 h at 200° C. (ASTM                                                           54      34                                             D 395 Method B) O-rings 214 (%)                                                Compression Set 70 h at 23° C.                                                                  44      30                                             O-rings 214 (%)                                                                ______________________________________                                    

The results show the same previous trends, in particular as regards the curing rate (v_(max)), compression set and the improved balance of the mechanical properties.

EXAMPLES 6-7

Examples 1-3 were repeated with the fluoroelastomer indicated below; the formulations are reported in Table 3 and the characteristics in Table 3A.

High fluorine tetrapolymer TECNOFLON® LX 5291 having composition:

    ______________________________________                                         VDF        32% by weight                                                       HFP        30% by weight                                                       MVE         7% by weight (perfluoromethylvinylether)                           TFE        31% by weight                                                       ______________________________________                                          (Fluorine 70% by weight), ML(1 + 10) at 121° C. = 31.             

                  TABLE 3                                                          ______________________________________                                         COMPOUND FORMULATION                                                                           EX. 6                                                                          (cfr) EX. 7                                                                    (phr) (phr)                                                    ______________________________________                                         Fluoroelastomer   100     100                                                  Bisphenol AF      2.7     --                                                   Accelerant (I)    1.35    0.3                                                  Adduct III        --      3.5                                                  MgO               3       3                                                    Ca(OH).sub.2      6       6                                                    MT Black          30      30                                                   ______________________________________                                    

                  TABLE 3A                                                         ______________________________________                                         characteristics of the compound of Table 3.                                                           Ex. 6                                                                          (cfr)                                                                               Ex. 7                                              ______________________________________                                         Rheometric properties                                                          Mooney Viscosity (ASTM D 1646-82)                                                                       78     74                                             ML(1 + 10) at 121° C. (in Mooney)                                       ODR 12' at 177° C. Arc +/- 3° (ASTM D2084-81)                    ML (lbf · in)   10     9                                              MH (lbf · in)   54     77                                             ts2 (sec)                225    246                                            t90 (sec)                350    390                                            v.sub.max (lbf · in/sec)                                                                       0.5    1.1                                            Mechanical properties (ASDTM D412-83)                                          Post curing @ 250° C. × 8 + 16 hours                              Modulus 100% (MPa)       5.3    6.0                                            Tensile strength (MPa)   11     13                                             Elongation at break (%)  220    203                                            Hardness Shore A         79     81                                             Compression Set 70 h at 200° C.                                                                  63     30                                             (ASTM D 395 Method B)                                                          O-rings 214 (%)                                                                ______________________________________                                    

By comparing the results it is noted the same trend of the previous examples: an improved processability (lower Mooney of the compound); improved crosslinking yield (MH) and crosslinking rate (v_(max)); the balance of the mechanical and elastomeric properties shows a clear improvement. 

We claim:
 1. Curable fluoroelastomeric compositions comprising:A) 100 parts (phr) copolymers or terpolymers based on VDF having a fluorine content of at least 67% by weight, and being comprised of 30 to 50% by weight of VDF, and 20 to 60% by weight of HFP, B) from 1 to 5 parts (phr) of an adduct between an accelerator and a curing agent, the accelerator being an onio-organic compound having a positive charge, the curing agent being a di- or polyhydroxy or di- or polythiol compound; the adduct being obtained by melting of the reaction product between said accelerator and said curing agent in a molar ratio of 1:2 to 1:5, or by melting of the adduct mixture having a molar ratio of 1:1 added with excess curing agent to obtain a molar ratio of 1:2 to 1:5.
 2. Compositions according to claim 1 wherein the other monomeric units are from 0 to 30% by weight of TFE and from 0 to 40 by weight of perfluoroalkylvinylethers.
 3. Compositions according to claim 1 wherein B) ranges from 2 to 4.5 phr and the adduct is 1:2 or 1:3.
 4. Compositions according to claim 1 wherein the accelerator forming the adduct cation is selected from the following classes:I) aminophosphonium [P(NR'R")_(n) (R¹ R² R³)_(4-n) ]⁺ wherein n is an integer from 1 to 3;R', R" and R¹ R² R³, equal or different from each other, are alkylic, cycloalkylic, arylic, arylalkylic, oxyalkylic or polyoxyalkylic groups having a free or esterified terminal --OH function; R' and R" contain from 1 to 7 carbon atoms and can be linked each other so as to form an heterocyclic ring with the nitrogen atom while R¹, R², R³ equal or different from each other contain from 1 to 18 carbon atoms; II) compounds having the formula

    Q.sup.+ (R.sup.a R.sup.b R.sup.c R.sup.d).sub.4

wherein Q is selected from nitrogen, phosphorus, arsenic, antimonium; III) compounds having formula:

    S.sup.+ (R.sup.a R.sup.b R.sup.c).sub.3

wherein in II) and III) R^(a), R^(b), R^(c), R^(d) are selected from alkyls, aryls, alkylaryls or their combinations, two of said free radicals can be linked each other and the Q or S atom can form an heterocyclic ring.
 5. Compositions according to claim 1 wherein the accelerator is selected from the quaternary phosphonium compounds containing at least a phosphorus atom linked with four simple covalent bonds to four organic radicals, the organic radicals generally containing from 2 to 8 carbon atoms, the organic radical, being linear or branched, optionally containing heteroatoms; or from aminophosphonium derivatives wherein the phosphorus atom is linked to a nitrogen atom and the other three covalent bonds are organic radicals wherein the carbon is linked to the phosphorus.
 6. Compositions according to claims 1 wherein the anion obtained from the curing agent is selected from the polyhydroxy or polythiol compounds from the following classes:X1) A(BH)_(m) wherein A is an arylene radical optionally substituted with alkylic groups, such radical including optionally alkyl groups has from 6 to 14 carbon atoms, B is oxygen or sulphur and m is equal to 2 or 3; X2) HB--R^(4a) --BHwherein R^(4a) is an alkylene or cycloalkylene radical optionally substituted with alkylic groups, such radical including optionally alkyl groups has from 6 to 18 carbon atoms and B is oxygen or sulphur; ##STR6## wherein R^(2a) is --SO--, --SO₂ --, --CO-- or a linear or branched alkylene radical containing from 1 to 9 carbon atoms and wherein the H atoms can be partially or wholly substituted with F atoms; X4) HOCH₂ --R^(3a) --CH₂ OHwherein R^(3a) is a perfluoropolyether or polyfluoroether chain, the average molecular weight by number Mn being from 360 to 2,000.
 7. Curable compositions according to claim 1 wherein to obtain the cured product it comprises:a) one or more acceptors of inorganic acids selected from those known in ionic vulcanisation of vinylidene fluoride copolymers, in amounts 1-40 parts for 100 parts fluoroelastomeric copolymer; b) one or more basic compounds selected from those known in ionic curing of vinylidenefluoride copolymers, in amounts from 0.5 to 10 parts for 100 parts of fluoroelastomeric copolymer.
 8. Curable compositions according to claim 1 wherein is present also an olefin in amounts from 0 to 25% by weight as ethylenically unsaturated monomer.
 9. Curable compositions according to claim 1 wherein the monomeric composition by weight is:

    ______________________________________                                                 VDF  40-50%                                                                    HFP   50-60%.                                                          ______________________________________                                    


10. Curable compositions according to claim 1 wherein the monomeric composition by weight is:

    ______________________________________                                                 VDF  30-50%                                                                    HFP  20-60%                                                                    TFE   10-30%.                                                          ______________________________________                                    


11. Curable composition according to claim 1, wherein the monomeric composition by weight is:

    ______________________________________                                         VDF                30-47%                                                      HFP (hexafluoropropene)                                                                           20-40%                                                      PAVE                3-20%                                                      TFE                 10-30%.                                                    ______________________________________                                    


12. Curable compositions according to claim 8, wherein the monomeric composition by weight is:

    ______________________________________                                                VDF    30-50%                                                                  HFP    20-58%                                                                  PAVE    0-40%                                                                  ethylene                                                                               2-15%                                                                  TFE      0-30%.                                                         ______________________________________                                    


13. A method which comprises preparing a fuel hose or a shaft seal from a composition according to claim
 1. 14. A method according to claim 13 wherein the monomeric composition by weight of the curable composition is:

    ______________________________________                                                 VDF  30-50%                                                                    HFP  20-60%                                                                    TFE   10-30%.                                                          ______________________________________                                    


15. A method which comprises preparing an O-ring for an injector from a composition according to claim
 1. 16. A method of use according to claim 15 wherein the monomeric compositions by weight of the curable composition is:

    ______________________________________                                                 VDF  30-50%                                                                    HFP  20-60%                                                                    TFE   10-30%.                                                          ______________________________________                                    


17. A curable fluoroelastomeric composition according to claim 1 wherein the acceleration indicated in B) is in amounts from 0.05 to 0.5 hr.
 18. A curable fluoroelastic composition according to claim 1 wherein the copolymers or terpolymers further comprise additional monomeric units derived from a monomer having ethylene unsaturation. 